CN110087702A - Shape memory polymer composite material for medical supplies 3D printing - Google Patents
Shape memory polymer composite material for medical supplies 3D printing Download PDFInfo
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- CN110087702A CN110087702A CN201780078829.5A CN201780078829A CN110087702A CN 110087702 A CN110087702 A CN 110087702A CN 201780078829 A CN201780078829 A CN 201780078829A CN 110087702 A CN110087702 A CN 110087702A
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- Prior art keywords
- shape memory
- polymer
- composite material
- printing
- hydroxyapatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/16—Materials with shape-memory or superelastic properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Dermatology (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Civil Engineering (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses the medical composite materials based on the thermoplastic polymer with bioactivity shape memory ceramics, wherein " hard " mutually includes crystalline phase, chemical cross-linking agent, Physical crosslinking agent and the bioactive ingredients of polymeric matrix, and " soft " mutually includes the amorphous phase and plasticizer of polymeric matrix.The composite material includes the hydroxyapatite bioactive filler that bioabsorbable polylactide polymer matrix and partial size are 100 to 1000 nanometers.Hydroxyapatite filling weight ratio is 15% to 35%.For reduce shape memory effect activationary temperature, the composite material includes plasticizer, i.e., weight ratio be 4.6% to 15% polyethylene glycol.For stabilizing mechanical performance, the composite material has cross-linked structure.The cross-linked structure and hard phase of the polymer material, i.e. hydroxyapatite nanoparticle can generate the recovery stress of 3Mpa under 98% shape recovery ratio.In addition, being added to polyethylene glycol plasticizer, the glass transition temperature of material is reduced, i.e. shape memory effect activates point.Shape memory effect activates in the range of 35 DEG C to 45 DEG C.The Young's modulus and modulus of elasticity in comperssion of the composite material are respectively 4GPa and 11GPa.The melt of the composite material shows high viscosity when being higher than fusing point (170 DEG C), to realize higher hierarchical application precision in the 3D printing of medical supplies.The solution have the advantages that providing a kind of polymer composites of 3D printing suitable for shape memory medical supplies.
Description
Technical field
Shape-memory polymer has many excellent better than memory shape metal alloy due to higher recoverable deformation
Point.The original shape of shape-memory polymer product can be by the spy for being lower than transition point (shape memory effect activationary temperature)
Determine to deform at temperature and be changed into temporary shapes, which can be glass transition temperature TgOr limitation polymer segment
Ambulant melting temperature Tm。
To show shape memory effect, polymer must have hard stationary phase and soft deformable phase.What shape was restored
Driving force is the ambulant variation of polymer form and is converted into from more orderly temporary distortion configuration and is more advantageous to thermodynamics
The conversion of configuration has higher entropy and lower interior energy.The conversion can be activated by outside stimulus, such as heat, electric field or
Magnetic field, light and moisture etc..From the perspective of practical application, use is most extensive and optimum shape memory effect activationary temperature
It is glass transition temperature Tg, the mobility for showing as polymer segment increases, so as to cause shape recovery.
In medical supplies, shape memory effect can have potential application in adaptive and self-anchored type bone implant.
Polyactide is a kind of thermoplastic polymer, due to its high elastic modulus, relatively low glass transition temperature Tg
And it is applicable to 3D printing application, therefore for bone implant using highly beneficial.The physical entanglement of long polyactide chain can fill
Work as hard phase, and the polymer chain between tangling can be drawn into temporary shapes during deformation.Have by being crosslinked or adding
The thin inorganic particle of high elastic modulus can improve polyactide recovery stress and recovery strain etc. as additional hard phase
Performance.From this, calcium phosphate granules restore highly beneficial to bone tissue.
The present invention relates to a kind of medical composite materials based on thermoplastic polymer, make pottery with shape memory bioactivity
Porcelain component additive can be used for manufacturing medical supplies by the fuse manufacturing technology (FFF) that 3D printing is implemented.
Technical background
A known Xiang Faming (US2013/0030122A1 polylactic acid cross-linked elastomer) describes the poly- friendship of the L- based on crosslinking
The method that ester or D- polyactide prepare polymer composition.
The shortcomings that foregoing invention, is the glass transition point T of -26 DEG C of polymer compositesgWith -224 DEG C of fusing point
Tm may be shape memory effect activationary temperature, be far below human body temperature.
(WO 2015110981A1 polyactide uses and manufactures heat seal tissue or plate container or packaging by a known Xiang Faming
Method) offer polyactide and poly butylene succinate (PBS) based polymer composite are provided and add multifunctional crosslinking
The method of element, such as triallyl isocyanurate (TAIC).
The shortcomings that foregoing invention, is that the polymer composites do not have shape memory effect.
A known Xiang Faming (method that US20150123314A1 is used to manufacture shape memory polymer material), which describes, to be mentioned
For the method for shape memory polymer material.By bioabsorbable polymer, (such as polyactide, gathers at polyglycolide the material
Caprolactone, polyurethane, polyacrylate, polymethacrylates, poly- butyl methyl acrylate or polyether-ether-ketone), biology pottery
Porcelain (such as calcium phosphate, tricalcium phosphate, hydroxyapatite, calcium carbonate, calcium sulfate, bio-vitric or glycolide) and polyethylene glycol system
At.
The shortcomings that foregoing invention, is that shape is restored not exclusively (being at optimum conditions 90%).
A known Xiang Faming (medical instrument that WO 2013050775A1 contains shape memory polymer composition) discloses
A kind of medical instrument based on shape memory polymer material.The polymer material is (poly- to hand over by bioabsorbable polymer
Ester, polyethylene glycol, polycaprolactone, polydioxanone, polyurethane, polyacrylate, polymethacrylates, poly- butyl methyl third
Olefin(e) acid ester or polyether-ether-ketone) and plasticizer (polyethylene glycol) be made.
The shortcomings that foregoing invention is compared with unfilled polyactide, without cross-linked structure and stable hard phase with
Higher recycling stress is provided.
Known invention (US2011/0144751A1 multimode shape-memory polymer and US 9308293B2 multimode shape memory
Polymer) disclose the polymer composites of the polymer and calcium phosphate ceramic that there is different molecular weight based on two kinds.
The shortcomings that foregoing invention be may be the polymer composites of shape memory effect activationary temperature vitrifying
Tg=-26 DEG C of transition point is far below human body temperature.In addition, the material does not have cross-linked structure to provide mechanical rigid.
Known invention (US2014/0236226A1 tailor-made polymer object and US 2015/0073476A1) discloses is handed over based on poly-
The polymer composites of ester and water-soluble plasticizer.
The shortcomings that foregoing invention, is incomplete (being at optimum conditions 90%) and the slowly shape of (in 24 hours)
Restore and does not have bioactive ingredients (calcium phosphate ceramic).
A known Xiang Faming (US 2015/0073476A1 shape memory polymer composition) describes the polymerization of polyactide base
Object composite material.
The shortcomings that foregoing invention, is incomplete (90%) and slowly the shape of (in 24 hours) is restored.
In addition, foregoing invention is not suitable for medical article 3D printing application.
The immediate counterpart of the present invention is the biodegradable shape-memory polymer of RU patent 2215542, description
Suitable for medical application and as treating or the biodegradable and biocompatible shape-memory polymer of diagnosis agent carrier
Composition.
The shortcomings that foregoing invention, is do not have bio-compatible reagent, i.e. calcium phosphate ceramic, and in the 3D of medical article
It not can be carried out hierarchical fusion in printing.Foregoing invention have another disadvantage that mechanical performance it is poor (elasticity modulus be lower than 100MPa,
And ultimate strength is lower than 20MPa).
Summary of the invention
The solution have the advantages that providing a kind of polymer composite suitable for shape memory medical supplies 3D printing
Material, has the feature that
Medical supplies 3D printing compatibility；
Keep the cross-linked structure of mechanical performance；
35 DEG C to 45 DEG C shape memory effect activationary temperatures；
The bioactive ingredients that partial size is 100 to 1000 nanometers；
When shape memory effect activates, recovery stress 3MPa, shape recovery ratio 98%；
Good tensile mechanical properties: 4GPa Young's modulus and 43MPa ultimate strength；
Good Compressive Mechanical Properties: 11GPa Young's modulus and 96MPa ultimate strength.
The following technical effects are achieved by the present invention: providing composite material based on thermoplastic polymer, is added with bioactivity
Shape memory ceramics ingredient, wherein " hard " mutually includes crystalline phase, chemically and physically crosslinking agent and the biology of polymeric matrix
Active constituent, and " soft " mutually includes the amorphous phase and plasticizer of polymeric matrix.
According to invention as described herein, the composite material includes bioabsorbable polylactide polymer matrix and partial size
For 100 to 1000 nanometers of hydroxyapatite bioactive filler.Hydroxyapatite filling weight ratio is 15% to 35%.For drop
Low profile memory effect activationary temperature, the composite material include plasticizer, i.e., weight ratio be 4.6% to 15% poly- second two
Alcohol.
Specific embodiment
For stabilizing mechanical performance, the composite material has cross-linked structure.The cross-linked structure of the polymer material and hard
Matter phase, i.e. hydroxyapatite nanoparticle can generate the recovery stress of 3Mpa under 98% shape recovery ratio.In addition, being added to
Polyethylene glycol plasticizer reduces material glass transition temperature, i.e. shape memory effect activates point.Shape memory effect is 35
It is activated within the scope of to 45 DEG C.The Young's modulus and modulus of elasticity in comperssion of the composite material are respectively 4GPa and 11GPa.It is described multiple
The melt of condensation material shows high viscosity when being higher than fusing point (170 DEG C), to realize in the 3D printing of medical supplies higher
Hierarchical application precision.
The polyactide content that weight ratio is 47% to 80% in the composite material is hard phase, soft phase and best addition polymerization
Necessary to object concentration coexists.If the weight ratio of the additive amount of polyethylene glycol plasticizer be higher than 15%, composite material it is strong
Degree and elasticity modulus are down to 40MPa and 4GPa or less respectively.But if the weight ratio of plasticizer additive amount is lower than 4.6%,
Plasticizing effect cannot be reached, shape memory effect activationary temperature is higher than 45 DEG C to 50 DEG C.The additive amount of hydroapatite particles
Weight ratio is lower than 15%, then cannot provide the bioactivity of material, and be reduced to the content of hard phase and be enough to generate
The recovery stress and shape recovery ratio of 1.5MPa or more is more than 95% level.Meanwhile excessive hydroxyapatite content (weight
35%) amount increases the brittleness of composite material than being higher than.Introduce weight ratio keeps structure crosslinking unknown lower than 0.4% crosslinking agent
It is aobvious, it is ensured that there are enough hard phases to realize shape memory effect when being higher than shape memory effect activationary temperature.On the other hand,
Rigid structure can be generated by introducing crosslinking agent of the weight ratio higher than 3%, and glass transition temperature is higher than 45 DEG C.Due to described compound
The excessive cross-linked structure of material, the composite material cannot be used for layering 3D printing.
The industry of polymer composites provided by the invention and medicine applicability are confirmed by following embodiment.
It is described with reference to the present invention, where figure 1 shows the poly- second that polymer material of the invention and weight ratio are 8%
The example of differential scanning calorimetry (DSC) curve of glycol.First phase transformation occur material glass transition point, i.e., 40.9
DEG C, it was demonstrated that shape memory effect activationary temperature is reduced to the point close to human body temperature.Fig. 2 has been illustrated imitates higher than shape memory
The growth of recovery stress when answering activationary temperature.Make the interim of the sample obtained at room temperature by 3D printing polymer composites
Shape distortion and stabilization are then heated to higher than shape memory effect activationary temperature and original shape recovery.Highest recovery stress
For 3MPa.Fig. 3 shows the compression figure example of the polymer composites for the hydroxyapatite for being 30% containing weight ratio.The limit is strong
Degree is higher than 80MPa, and Young's modulus is more than 10.8GPa.Fig. 4 shows the polymer for the hydroxyapatite for being 30% containing weight ratio
The tensile diagram of composite material.Tensile strength is higher than 60MPa, and Young's modulus is more than 4.0GPa.
Embodiment 1
Ingeo 4032D polyactide (Natureworks LLC, the U.S.), the GAP 85-D hydroxyl that average particle size is 1000nm
The polyethylene glycol (OOO polymer) that base apatite powder (NPO Polystom) and molecular weight are 4000g/mol is used as raw material.
Final polymer product contains the polyactide that weight ratio is 47%, the hydroxyapatite that weight ratio is 35% and weight ratio
15% polyethylene glycol.Polyactide structure and Evonik TAIC triallyl isocyanurate (weight ratio 3%) are crosslinked.Institute
The glass transition temperature for stating material is 35 DEG C, recovery stress 2.5MPa, shape recovery ratio 98%, the polymer of 3D printing
The compression strength of composite sample is 70MPa, modulus of elasticity in comperssion 9GPa.
Embodiment 2
Ingeo 4032D polyactide (Natureworks LLC, the U.S.), the GAP 85-D hydroxyl that average grain diameter is 100nm
The polyethylene glycol (OOO polymer) that apatite powder (NPO Polystom) and molecular weight are 4000g/mol is used as raw material.Finally
Polymer product to contain hydroxyapatite that polyactide, weight ratio that weight ratio is 80% are 15% and weight ratio be 4.6%
Polyethylene glycol.Polyactide structure and PERKADOX BC-FF cumyl peroxide (weight ratio 0.4%) are crosslinked.The material
The glass transition temperature of material is 45 DEG C, and the polymer of recovery stress 1.7MPa, shape recovery ratio 96%, 3D printing are compound
The compression strength of material sample is 80MPa, modulus of elasticity in comperssion 7GPa.
1 compressor mechanical test result of table
Claims (2)
1. one kind being capable of shape memory polymer composite material comprising answered based on biodegradable and biocompatible polymer
" hard " of condensation material mutually and " soft " phase, wherein " hard " of the polymer composites mutually includes polymeric matrix
Crystalline phase, chemical cross-linking agent, Physical crosslinking agent and partial size be 100-1000nm the hydroxy-apatite as bioactive ingredients
Stone, " soft " the mutually amorphous phase including polymeric matrix and the polyethylene glycol as plasticizer, component ratio (wt.%) is such as
Under:
47-80 polyactide,
15-35 hydroxyapatite,
4.6-15 polyethylene glycol,
0.4-3.0 crosslinking agent.
2. polymer composites as described in claim 1, wherein the chemical cross-linking agent is triallyl isocyanurate
Or cumyl peroxide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2016149740 | 2016-12-19 | ||
| RU2016149740A RU2631890C1 (en) | 2016-12-19 | 2016-12-19 | Polymer composite with shape memory effect for 3d-printing of medical equipment |
| PCT/RU2017/000929 WO2018117907A1 (en) | 2016-12-19 | 2017-12-11 | Shape memory polymer composite for 3d printing of medical items |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110087702A true CN110087702A (en) | 2019-08-02 |
Family
ID=60040580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780078829.5A Pending CN110087702A (en) | 2016-12-19 | 2017-12-11 | Shape memory polymer composite material for medical supplies 3D printing |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN110087702A (en) |
| DE (1) | DE112017006358T5 (en) |
| EA (1) | EA036376B1 (en) |
| RU (1) | RU2631890C1 (en) |
| WO (1) | WO2018117907A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2679127C1 (en) * | 2018-06-14 | 2019-02-06 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | Composite for 3d-printing of medical products |
| RU2679632C1 (en) * | 2018-06-14 | 2019-02-12 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | Composite for 3d-printing of medical products |
| EP3822006A1 (en) | 2019-11-14 | 2021-05-19 | Rolls-Royce Corporation | Fused filament fabrication of shape memory alloys |
| KR102258272B1 (en) | 2020-05-11 | 2021-05-31 | 주식회사 엠오피(M.O.P Co., Ltd.) | Light polymerised 3d printing method using self healing photopolymer |
| CN113368311A (en) * | 2021-04-14 | 2021-09-10 | 成都理工大学 | Hydroxyapatite/polyurethane porous bone repair material with shape memory |
| CN113502038A (en) * | 2021-07-21 | 2021-10-15 | 珠海市三绿实业有限公司 | Memory 3D printing supplies lines with wooden feel |
| CN115230143A (en) * | 2022-06-24 | 2022-10-25 | 南昌大学第二附属医院 | Degradable high-ceramic-particle-concentration flexible 3D printing biological scaffold method |
| CN115558248B (en) * | 2022-11-01 | 2023-07-21 | 桂林电子科技大学 | Light/heat driven shape memory and self-repairing functional material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6160084A (en) * | 1998-02-23 | 2000-12-12 | Massachusetts Institute Of Technology | Biodegradable shape memory polymers |
| US20150123314A1 (en) * | 2011-10-05 | 2015-05-07 | Smith & Nephew Plc | Process for the manufacture of shape memory polymer material |
-
2016
- 2016-12-19 RU RU2016149740A patent/RU2631890C1/en active
-
2017
- 2017-12-11 EA EA201900311A patent/EA036376B1/en not_active IP Right Cessation
- 2017-12-11 DE DE112017006358.2T patent/DE112017006358T5/en not_active Withdrawn
- 2017-12-11 WO PCT/RU2017/000929 patent/WO2018117907A1/en active Application Filing
- 2017-12-11 CN CN201780078829.5A patent/CN110087702A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6160084A (en) * | 1998-02-23 | 2000-12-12 | Massachusetts Institute Of Technology | Biodegradable shape memory polymers |
| US20150123314A1 (en) * | 2011-10-05 | 2015-05-07 | Smith & Nephew Plc | Process for the manufacture of shape memory polymer material |
Also Published As
| Publication number | Publication date |
|---|---|
| DE112017006358T5 (en) | 2019-08-29 |
| EA036376B1 (en) | 2020-11-02 |
| EA201900311A1 (en) | 2019-11-29 |
| WO2018117907A1 (en) | 2018-06-28 |
| RU2631890C1 (en) | 2017-09-28 |
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Application publication date: 20190802 |